EP0916625A1 - Process to prepare moulded shaped translucent lithium-di-silicate glass ceramic products - Google Patents
Process to prepare moulded shaped translucent lithium-di-silicate glass ceramic products Download PDFInfo
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- EP0916625A1 EP0916625A1 EP98250392A EP98250392A EP0916625A1 EP 0916625 A1 EP0916625 A1 EP 0916625A1 EP 98250392 A EP98250392 A EP 98250392A EP 98250392 A EP98250392 A EP 98250392A EP 0916625 A1 EP0916625 A1 EP 0916625A1
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- Prior art keywords
- glass ceramic
- glass
- product
- ceramic product
- dental
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/16—Refractive index
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/78—Pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/804—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising manganese oxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/807—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising magnesium oxide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/822—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising rare earth metal oxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/824—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising transition metal oxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/833—Glass-ceramic composites
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
Definitions
- the invention relates to a method for producing shaped translucent lithium disilicate glass ceramic products, which can be produced as blanks, in particular by plastic deformation under the influence of pressure and heat or machining to shaped translucent dental products can be processed with high strength.
- Lithium disilicate glass ceramics are known from the prior art.
- EP-B-536 479 describes self-glazed lithium disilicate glass ceramic articles, but these are not intended for dental purposes.
- the glass ceramics also contain no La 2 O 3 , and it is also not described to produce blanks from the glass ceramic which, after processing, are subjected to a further heat treatment in order to complete the crystallization. It is also necessary to carry out the heat treatment at a very low heating rate of 5K / min in order to avoid stresses in the structure of the glass ceramic.
- the glass ceramic is primarily for the production of tableware provided, which naturally has only a low translucency Has.
- EP-B-536 572 also describes lithium disilicate glass ceramics which contain no La 2 O 3 . By sprinkling a finely divided colored glass on their surface, they are given structure and color, and they are used as lining elements for building purposes.
- lithium disilicate glass ceramics which contain calcium oxide for improving flow and as a special nucleating agent platinum and niobium oxide for producing very fine and uniform crystals. Even if the glass ceramic can be produced in the form of blanks which have not yet completely crystallized, it is nevertheless free of La 2 O 3 .
- WO-A-95/32678 and US-A-5,507,981 describe lithium disilicate glass ceramics, which when using a special compressible Crucibles by hot pressing to shaped dental products can be processed.
- the glass ceramic Materials heated so far that no more crystals in the melted Material are present, otherwise the viscosity for the Pressing to the dental product is too high.
- the glasses used show a very high crystal growth rate, so that great in heat treatment Crystals are created that form the structure of the glass ceramic disturb and accordingly to products with little skill to lead.
- US Pat. No. 4,515,634 discloses a lithium disilicate glass ceramic which is suitable for producing dental crowns and bridges, but which does not contain any La 2 O 3 .
- the glass ceramics described in FR-A-2 655 264 are also free of La 2 O 3 . They contain lithium oxide and silicon oxide as well as very large amounts of MgO and are suitable for the manufacture of dental prostheses.
- Blanks made of sintered ceramic are also from the prior art known based on leucite, feldspar or mica, the using computer-aided milling processes for dental products are processed. However, these products only have low strength, which is why these materials are suitable for high loads Dental restorations.
- the known lithium disilicate glass ceramics show shortcomings in their further processing into shaped products, because they are used in their plastic state from undesirable temperatures and elevated pressures strong reaction with the investment used in the pressing occurs. Further processing of the glass ceramics by machining, such as milling, is due to the strength and Toughness of glass ceramics is usually not satisfactory Feasible dimensions.
- the conventional show further Lithium disilicate glass ceramics are often not those for dental products required high strength and optical Properties, such as high translucency, and they lack in many cases also on the for use as a dental material required chemical stability, which is in the oral cavity is constantly flushed with a wide variety of fluids.
- the invention is accordingly based on the object of a method for the production of shaped translucent lithium disilicate glass ceramic products to provide that a high chemical stability, a low density of defects and a high translucency with good mechanical properties have and during further processing by pressing in plastic state a little reaction with the inserted Investment material show, and the glass ceramic products also in Formed blanks with a low degree of crystallization that can be easily machined, like machining processes, shaped in the desired manner and by subsequent heat treatment to a high strength Glass ceramic product can be converted.
- the invention also relates to the shaped glass ceramic products according to claims 13 to 15, the use according to Claim 16 and the shaped dental products according to the claims 17 to 19.
- process step (a) there is a melt of an initial glass generated, for which suitable starting materials, e.g. Carbonates, Oxides, phosphates and fluorides, intimately mixed and heated to temperatures of in particular 1200 to 1600 ° C. become.
- suitable starting materials e.g. Carbonates, Oxides, phosphates and fluorides
- the produced glass melt to form a glass granulate in Poured water and the glass granules obtained again Temperatures of in particular 1200 to 1600 ° C for 1 to 4 Hours are melted.
- the melt of the starting glass preferably contains at least one of the following further components: component % By weight ZrO 2 0 to 10.0 K 2 O 0 to 13.5 P 2 O 5 0 to 11.0 Color and fluorescence components 0 to 8.0 Additional components 0 to 6.0
- component % By weight SiO 2 57.0 to 75.0 Al 2 O 3 0 to 2.5 La 2 O 3 0.1 to 4.0 MgO 0.1 to 5.0 ZnO 0 to 6.0, especially 0.1 to 5.0 ZrO 2 0 to 8.0, especially 0.1 to 8.0 K 2 O 0 to 9.0, in particular 0.5 to 7.0 Li 2 O 13.0 to 19.0 P 2 O 5 0 to 8.0, in particular 0.5 to 8.0 Color and fluorescence components 0.1 to 8.0 Additional components 0 to 3.0.
- Oxides of f-elements can be used as the color component or fluorescence component. At least one of the following compounds is preferably used.
- component % By weight CeO 2 0.1 to 5.0 V 2 O 5 0.01 to 1.0 Fe 2 O 3 0.01 to 1.0 MnO 2 0.01 to 3.0 TiO 2 0.01 to 5.0 Y 2 O 3 0.01 to 2.0 He 2 O 3 0.001 to 2.0 Tb 2 O 3 0.001 to 2.0 Eu 2 O 3 0.001 to 2.0 Yb 2 O 3 0.001 to 2.0 Gd 2 O 3 0.001 to 2.0 Nd 2 O 3 0.001 to 2.0 Pr 2 O 3 0.001 to 2.0 Dy 2 O 3 0.001 to 2.0 Ag 2 O 0.01 to 2.0 SnO 2 0.01 to 3.0 Ta 2 O 5 0.001 to 2.0
- the special in the process according to the invention as color or Fluorescence components that can be used ensure an easy adjustment of the color of the glass ceramic product to the respective application. This is of particular importance when the glass ceramic products are used as dental products should be whose color matches that of the natural tooth material of the respective patient must be specially adapted. That with The color spectrum that can be achieved with these special oxides ranges from very high light tones to strong gray-brown tones e.g. at devitalen Tooth stumps. This is due to any existing fluorescent components imitates the fluorescence of the natural tooth material.
- a particular advantage of the color and Fluorescence components is that they are the structure of the generated Glass ceramic products do not interfere in the way that inhomogeneous Materials with high defect density and high porosity be generated.
- the starting glass can also contain additional components, for which B 2 O 3 , Na 2 O, BaO, F and / or SrO are particularly suitable.
- the melt of the starting glass preferably consists of the mentioned components in the specified amounts.
- stage (b) is the melt of the starting glass in the molded and cooled as desired. This is where the molding takes place especially by pouring the melt into a desired one Shape. It is further possible that even after pouring the melt is compressed by a pressure to achieve particularly good homogeneity and accurate imaging. This can be done in such a way that a glass drop brought into the desired shape and then by pressing is compressed.
- the melt is cooled in a controlled manner Way to deal with rapid temperature changes Tensions in the structure and possibly resulting from it To prevent cracks and cracks. As a rule, therefore Melt poured into preheated molds or in an oven cooled slowly.
- step (c) the molded glass product formed subjected to at least one heat treatment in this way to cause its crystallization.
- the process step is a molded one that is present as a blank Glass ceramic product received.
- This blank usually has the shape of a small cylinder or a rectangular block.
- the heat treatment is preferably carried out at a temperature of less than 1000 and especially less than 900 ° C. Doing so the molded glass product preferably into one already on the mentioned temperature heated furnace introduced. In contrast to conventional materials it is not necessary to use one slow heating rate to choose to voltages to exclude. For this beneficial behavior is obvious the special composition and production method of the invention Materials responsible.
- the degree of crystallization and the crystal size in this glass ceramic blank can be varied within a very wide range by the type of heat treatment selected.
- the ceramization process takes place via the mechanism of volume crystallization, and volume nucleating agents, such as, for example, P 2 O 5 , play an important role in the formation of crystals which are finely distributed in the structure.
- the final glass ceramic product e.g. a dental bridge or a dental crown in particular the following two options (d1) and (d2).
- step (d1) the present as a blank Glass ceramic product at a temperature of 700 to 1200 ° C and by applying pressure, in particular from 8 to 40 bar a glass ceramic product of the desired geometry be deformed.
- pressure in particular from 8 to 40 bar a glass ceramic product of the desired geometry be deformed.
- the one in particular Press furnace used is from the Ivoclar AG, Liechtenstein.
- the glass ceramic product which is in the form of a blank, can advantageously be processed by pressing in the plastic state into a glass ceramic product of the desired geometry, in particular a dental product, such as a dental restoration.
- the glass ceramic product is also possible to use the glass ceramic product as a blank in stage (d2) by machining, in particular CAD / CAM-based milling devices, to a glass ceramic product to process the desired geometry. So that's a so-called "Chair-side" treatment for the dentist possible.
- a Glass ceramic blank used which is not yet complete is crystallized, but e.g. only as a germ-containing glass blank or glass ceramic blank with very small crystals is present.
- Such has not yet fully crystallized Glass ceramic blanks have the particular advantage that they are in much easier than conventional glass ceramics desired by machine to the finished glass ceramic product Geometry can be processed.
- the heat treatment carried out in step (c) to be carried out at a temperature of 400 to 900 ° C.
- the degree of crystallinity used Glass ceramic blanks to the type of cutting desired Editing can be adjusted to make this as easy as possible to be able to.
- the molded glass ceramic product obtained After the subsequent machining in stage (d2) the molded glass ceramic product obtained then at least one further heat treatment, especially at 700 to 900 ° C, subjected to further crystallization and thus solidification of the glass ceramic product. Through this further heat treatment are breaking strength, color and improves translucency.
- the finished glass ceramic product of the desired geometry present after further processing, in particular in stages (d1) and (d2), can finally be provided with a coating, which is particularly advantageous when it is used in the dental field.
- a ceramic, a sintered ceramic, a glass ceramic, preferably an apatite glass ceramic, a glass, a glaze and / or a composite are particularly suitable as coatings.
- Coatings which have a sintering temperature of 650 to 950 ° C. and a linear thermal expansion coefficient which is smaller than that of the glass ceramic product to be coated are advantageous.
- Coatings whose linear thermal expansion coefficient does not differ by more than ⁇ 3.0 ⁇ 10 -6 K -1 from that of the substrate are particularly advantageous.
- a coating is applied in particular by sintering.
- the glass ceramic product containing the lithium disilicate glass ceramic is brought into a temperature range which lies above the transformation point of the residual glass matrix of the glass ceramic.
- Conventional lithium disilicate glass ceramics are often deformed in an undesirable manner because they have insufficient temperature stability.
- the glass ceramic product produced according to the invention has an excellent temperature stability, for which the content of La 2 O 3 and optionally Al 2 O 3 in the stated amounts is particularly responsible.
- the glass ceramic products produced according to the invention are due to their properties, especially for use as dental products or components of these are suitable.
- Have so preferred glass ceramic products have a 3-point bending strength more than 400 MPa; if it is produced according to process variant (d1) be, and more than 250 MPa if according to process variant (d2) can be produced. That to determine the 3-point bending strength
- the procedure used is in the examples explained.
- the glass ceramic product according to the invention usually has one CR value from 0.05 to 0.9 and preferably from 0.1 to 0.75, each gmeasured with a sample thickness of 1.2 mm.
- the glass ceramic product according to the invention is distinguished by excellent acid resistance, which is preferably less than 100 ⁇ g / cm 2 loss in mass. This loss of mass was determined according to the method explained in the examples, in which the glass ceramic is treated with aqueous acetic acid for a certain period of time, and the loss of mass found after the treatment serves as a measure of the acid resistance.
- Preferred molded dental products that the invention Glass ceramic product, dental restorations are like e.g. an inlay, an onlay, a bridge, a pen structure, an Veneer, a veneer, a facet, a crown or a Partial crown.
- Such shaped dental products are preferred which are used as There are blanks, i.e. where there is still further processing to the final dental product, e.g. after steps (d1) and (d2) takes place.
- Such blanks can be used in different ways there are forms adapted to the respective further processing methods, such as. small cylinders or rectangular blocks.
- a total of 20 different glass ceramic products according to the invention were produced with the chemical compositions given in Table I by carrying out steps (a) to (c) of the process described.
- This example describes the preparation of an inventive Glass ceramic blank, which is used to manufacture a individually formable all-ceramic dental product, e.g. a crown or a multi-unit bridge. On the Dental product can then also have an adapted dental sintered ceramic be burned.
- a starting glass with the in Table I for Example 14 chemical composition prepared.
- a mixture of appropriate oxides, carbonates and Phosphates mixed in a ball mill and in a platinum / rhodium crucible at a temperature of 1500 ° C and one Homogenization time of 2 hours melted.
- the received Glass melt was granulated by pouring it into water, and the Glass frit formed was dried. Then the glass frit ground again in a ball mill and again at 1500 ° C and a homogenization time of 2 hours melted.
- the obtained homogeneous, transparent and slightly yellow colored The melt was then preheated to 500 ° C Steel mold cast into cylindrical bars, which are in an oven cooled slowly from room temperature to 500 ° C were.
- the glass rods obtained became samples of 2 g, 3 g and sawed 4 g and then heat treated at 870 ° C for 30 minutes, to form the corresponding glass ceramic blanks.
- the cooled glass rods were directly in the to 870 ° C preheated oven. A slow heating rate was not required.
- the glass ceramic blanks obtained had comparable optical Properties such as Translucency, staining and turbidity, such as conventional dental ceramic sales products, e.g. IPS Empress blanks by Ivoclar AG, Liechtenstein.
- the determination of the 3-point bending strength was then also carried out according to ISO 6872-1995 E "Dental Ceramic" at a feed rate of load application of 0.5 mm / min and a span of the test equipment of 15 mm.
- the flexural strength determined under these conditions was 408 ⁇ 63 MPa.
- the glass ceramic blanks obtained were pressed into the sample geometry desired for the respective test under vacuum in the viscous state using the hot pressing method according to EP-A-231 773 and the press furnace likewise described there.
- the standby temperature of the press furnace was 800 ° C, the heating rate up to the press temperature 60 ° C / min, the press temperature 910 ° C, the holding time at the press temperature 15 minutes and the press pressure display 5 bar.
- the mold was cooled in air and the shaped glass ceramic products obtained were removed from the mold by sandblasting with Al 2 O 3 powder and glass beads.
- the products had the following properties.
- test specimens with a diameter of 16 mm and a sample thickness of 1.4 mm.
- the final sample height / thickness was 1.2 ⁇ 0.025 mm.
- the contrast value CR Y b / Y w was then calculated from the determined values Y b and Y w and was 0.63.
- this glass ceramic product was suitable as an all-ceramic dental product, the optically corresponds to the specifications of a natural tooth.
- the Color intensity and tint due to the concentration of the coloring Oxides could be adjusted.
- a translucent to transparent dental sintered glass ceramic with an expansion coefficient of 9.5 ⁇ 10 -6 K -1 (100 to 400 ° C.) could be applied as a coating on the translucent glass ceramic product that can be used as the framework material.
- the dental sintered glass ceramic was sintered in layers onto the glass ceramic product under vacuum at 760 ° C, which led to translucent all-ceramic dental restorations that meet the high aesthetic requirements for such products.
- the 3-point bending strength was measured on hot-pressed glass ceramic rods according to the procedure used above for the blanks certainly. A 3-point bending strength of 450 ⁇ 85 MPa determined.
- cylindrical glass ceramic samples with a diameter of 6 mm and a length of 20 mm were hot pressed.
- the coefficient of expansion determined for these samples in the temperature range from 100 to 500 ° C. was 10.8 ⁇ 10 -6 K -1 .
- glass ceramic rods with the dimensions 20 ⁇ 4.4 ⁇ 1.4 mm 3 were hot-pressed and then ground on all sides with SiC wet abrasive paper (1000 grit). With a diamond cutting disc (0.2 mm thick), the samples were notched on one side up to the middle to a depth of 2.2 mm and then according to DIN 51 109 with an outer span of 15 mm and a feed rate of load application of 0.5 mm / min checked using a 4-point bending arrangement. The K IC value determined was 3.0 ⁇ 0.3 MPa ⁇ m.
- disk-shaped glass ceramic samples with a diameter of 15 mm and a thickness of 1.5 mm were hot pressed and then ground on all sides with SiC wet sanding paper (1000 grit).
- the area-related mass loss of these samples determined in accordance with ISO 6872-1995 E “Dental Ceramic”, was determined after 16 hours of storage in 4% by volume aqueous acetic acid solution. The value was 36 ⁇ g / cm 2 and was significantly below the standard value for dental ceramics of 2000 ⁇ g / cm 2 .
- This example describes the preparation of an inventive Glass ceramic blanks made by machining and then again heat treatment to an individual molded all-ceramic dental product, e.g. a crown or a multi-unit bridge that is processed on top of that an adapted translucent to transparent dental sintered ceramic can be burned.
- an individual molded all-ceramic dental product e.g. a crown or a multi-unit bridge that is processed on top of that an adapted translucent to transparent dental sintered ceramic can be burned.
- the dental product was manufactured using a CAD / CAM process, such as. CEREC 2®, from Siemens AG.
- a starting glass with the composition given in Table I for Example 7 was produced.
- a mixture of oxides, carbonates and phosphates was mixed in a ball mill and melted in a platinum / rhodium crucible at a temperature of 1500 ° C. and a homogenization time of 2 hours.
- the glass melt was fritted by pouring it into water and, after drying, the frit was ground in a ball mill and melted again at 1500 ° C. and a homogenization time of 2 hours.
- the homogeneous, transparent and slightly yellow-colored melt obtained was then poured into a steel mold preheated to 500 ° C.
- the glass ceramic blanks had a violet-white color. They had one using the procedure described in Example 21 determined CR of 0.36.
- the 3-point bending strength determined according to Example 21 for the glass ceramic blanks was 171 ⁇ 20 MPa.
- the simply heat-treated glass ceramic blanks were made using a computer-controlled milling machine for dental ceramics Restorations, e.g. Crowns, processed. Due to the relatively low strength and toughness of the glass ceramic blanks the processing proved to be easy to carry out. In comparison to known milling ceramics, they called you less tool wear, and it formed fewer breakouts, indicating the finer structure and freedom from defects is traceable.
- the milled dental restoration was then another Subject to heat treatment at 760 ° C for 1 h. This Temperature was chosen because there was no risk of deformation of the scaffold. This additional heat treatment led to further crystallization and thus change the properties of the restoration.
- the received two Treated glass ceramics had the following properties.
- the glass ceramic was translucent and through the use of glass-staining oxides in toothpaste tinted in the starting glass.
- the 3-point flexural strength determined according to Example 21 Glass ceramic was 272 ⁇ 24 MPa.
- test specimens measuring 30 ⁇ 4 ⁇ 3 mm 3 were sawn from double heat-treated solid blocks.
- the coefficient of expansion determined for these samples in the temperature range from 100 to 500 ° C. was 10.9 ⁇ 10 -6 K -1 .
- Example 21 The according to Example 21 on rods made of double thermal The fracture toughness determined in the treated solid blocks was 2.1 ⁇ 0.1 MPa ⁇ m.
- the acid resistance determined according to Example 21 on samples of double-heat-treated glass ceramic was 16 ⁇ g / cm 2 and was thus clearly below the standard value for dental ceramic materials of 2000 ⁇ g / cm 2 and lower than that of conventional dental framework materials.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von geformten transluzenten Lithiumdisilikat-Glaskeramik-Produkten, welche als Rohlinge herstellbar sind, die insbesondere durch plastische Verformung unter Druck- und Wärmeeinwirkung oder spanende Bearbeitung zu geformten transluzenten Dentalprodukten mit hoher Festigkeit verarbeitet werden können.The invention relates to a method for producing shaped translucent lithium disilicate glass ceramic products, which can be produced as blanks, in particular by plastic deformation under the influence of pressure and heat or machining to shaped translucent dental products can be processed with high strength.
Lithiumdisilikat-Glaskeramiken sind aus dem Stand der Technik bekannt. So werden in der EP-B-536 479 selbstglasierte Lithiumdisilikat-Glaskeramik-Gegenstände beschrieben, die jedoch nicht für dentale Zwecke vorgesehen sind. Die Glaskeramiken enthalten zudem kein La2O3, und es wird ebenfalls nicht beschrieben, Rohlinge aus der Glaskeramik herzustellen, die nach Bearbeitung einer weiteren Wärmebehandlung zur Vervollständigung der Kristallisation unterworfen werden. Auch ist es erforderlich, die Wärmebehandlung bei sehr geringer Aufheizrate von 5K/min durchzuführen, um Spannungen im Gefüge der Glaskeramik zu vermeiden. Lithium disilicate glass ceramics are known from the prior art. For example, EP-B-536 479 describes self-glazed lithium disilicate glass ceramic articles, but these are not intended for dental purposes. The glass ceramics also contain no La 2 O 3 , and it is also not described to produce blanks from the glass ceramic which, after processing, are subjected to a further heat treatment in order to complete the crystallization. It is also necessary to carry out the heat treatment at a very low heating rate of 5K / min in order to avoid stresses in the structure of the glass ceramic.
Weiter ist die Glaskeramik primär zur Herstellung von Tafelgeschirr vorgesehen, welches naturgemäß eine nur geringe Transluzenz hat.Furthermore, the glass ceramic is primarily for the production of tableware provided, which naturally has only a low translucency Has.
Auch die EP-B-536 572 beschreibt Lithiumdisilikat-Glaskeramiken, die kein La2O3 enthalten. Durch Aufstreuen eines feinteiligen gefärbten Glases auf ihre Oberfläche erhalten sie Struktur und Färbung, und sie werden als Auskleidungselemente für Bauzwecke eingesetzt.EP-B-536 572 also describes lithium disilicate glass ceramics which contain no La 2 O 3 . By sprinkling a finely divided colored glass on their surface, they are given structure and color, and they are used as lining elements for building purposes.
In der US-A-4,189,325 werden Lithiumdisilikat-Glaskeramiken offenbart, die zwingend Calciumoxid zur Fließverbesserung sowie als besondere Keimbildner Platin und Nioboxid zur Erzeugung von sehr feinen und einheitlichen Kristallen enthalten. Auch wenn die Glaskeramik in Form von noch nicht vollständig kristallisierten Rohlingen erzeugt werden kann, so ist sie dennoch frei von La2O3.In US-A-4,189,325 lithium disilicate glass ceramics are disclosed, which contain calcium oxide for improving flow and as a special nucleating agent platinum and niobium oxide for producing very fine and uniform crystals. Even if the glass ceramic can be produced in the form of blanks which have not yet completely crystallized, it is nevertheless free of La 2 O 3 .
Die WO-A-95/32678 und US-A-5,507,981 beschreiben Lithiumdisilikat-Glaskeramiken, die bei Einsatz eines speziellen verpreßbaren Tiegels durch Heißpressen zu geformten Dentalprodukten verarbeitet werden können. Allerdings werden die glaskeramischen Materialien soweit erhitzt, daß keine Kristalle mehr im geschmolzenen Material vorliegen, da sonst die Viskosität für das Verpressen zu dem Dentalprodukt zu hoch ist. Untersuchungen haben gezeigt, daß beim Verpressen der beschriebenen Materialien mittels des in der EP-A-231 773 beschriebenen Verfahrens sowie unter Verwendung des dort offenbarten Preßofens eine unerwünscht starke Reaktion mit der eingesetzten Einbettmasse auftritt. Außerdem zeigen die eingesetzten Gläser eine sehr hohe Kristallwachstumsgeschwindigkeit, so daß bei der Wärmebehandlung große Kristalle entstehen, die das Gefüge der erzeugten Glaskeramik stören und demgemäß zu Produkten mit nur geringer Fertigkeit führen. WO-A-95/32678 and US-A-5,507,981 describe lithium disilicate glass ceramics, which when using a special compressible Crucibles by hot pressing to shaped dental products can be processed. However, the glass ceramic Materials heated so far that no more crystals in the melted Material are present, otherwise the viscosity for the Pressing to the dental product is too high. Have investigations shown that when pressing the materials described by means of the method described in EP-A-231 773 and using the press furnace disclosed there an undesirable strong reaction occurs with the investment used. In addition, the glasses used show a very high crystal growth rate, so that great in heat treatment Crystals are created that form the structure of the glass ceramic disturb and accordingly to products with little skill to lead.
Weiter sind aus der DE-C-1 421 886 Glaskeramiken auf der Basis von SiO2 und Li2O bekannt, welche große Mengen an physiologisch sehr bedenklichem Arsenoxid enthalten.Furthermore, from DE-C-1 421 886 glass ceramics based on SiO 2 and Li 2 O are known which contain large amounts of arsenic oxide which is physiologically very questionable.
In der US-A-4,515,634 wird eine zur Herstellung von Dentalkronen und -brücken geeignete Lithiumdisilikat-Glaskeramik offenbart, die jedoch keinerlei La2O3 enthält.US Pat. No. 4,515,634 discloses a lithium disilicate glass ceramic which is suitable for producing dental crowns and bridges, but which does not contain any La 2 O 3 .
Auch die in FR-A-2 655 264 beschriebenen Glaskeramiken sind frei von La2O3. Sie enthalten Lithiumoxid und Siliciumoxid sowie sehr große Mengen an MgO und sind zur Herstellung von Dentalprothesen geeignet.The glass ceramics described in FR-A-2 655 264 are also free of La 2 O 3 . They contain lithium oxide and silicon oxide as well as very large amounts of MgO and are suitable for the manufacture of dental prostheses.
Weiter sind aus dem Stand der Technik auch Rohlinge aus Sinterkeramik auf Basis von Leucit, Feldspat oder Glimmer bekannt, die mittels computer-gestützter Fräsverfahren zu Dentalprodukten verarbeitet werden. Diese Produkte besitzen allerdings nur geringe Festigkeit, weshalb sich diese Materialien für hochbelastete Dentalrestaurationen nicht durchgesetzt haben.Blanks made of sintered ceramic are also from the prior art known based on leucite, feldspar or mica, the using computer-aided milling processes for dental products are processed. However, these products only have low strength, which is why these materials are suitable for high loads Dental restorations.
Die bekannten Lithiumdisilikat-Glaskeramiken zeigen Unzulänglichkeiten bei ihrer Weiterverarbeitung zu geformten Produkten, da bei ihrer Verarbeitung im plastischen Zustand unter Einsatz von erhöhten Temperaturen und erhöhten Drucken eine unerwünscht starke Reaktion mit der bei dem Verpressen eingesetzten Einbettmasse auftritt. Eine Weiterverarbeitung der Glaskeramiken durch spanende Bearbeitung, wie Fräsen, ist infolge der Festigkeit und Zähigkeit der Glaskeramiken in der Regel nicht in zufriedenstellendem Maße durchführbar. Weiter zeigen die herkömmlichen Lithiumdisilikat-Glaskeramiken häufig nicht die für Dentalprodukte erforderlichen hohen Festigkeiten und optischen Eigenschaften, wie hohe Transluzenz, und ihnen mangelt es in vielen Fällen auch an der für den Einsatz als Dentalmaterial erforderlichen chemischen Stabilität, welches in der Mundhöhle permanent mit Fluiden unterschiedlichster Art umspült wird. The known lithium disilicate glass ceramics show shortcomings in their further processing into shaped products, because they are used in their plastic state from undesirable temperatures and elevated pressures strong reaction with the investment used in the pressing occurs. Further processing of the glass ceramics by machining, such as milling, is due to the strength and Toughness of glass ceramics is usually not satisfactory Feasible dimensions. The conventional show further Lithium disilicate glass ceramics are often not those for dental products required high strength and optical Properties, such as high translucency, and they lack in many cases also on the for use as a dental material required chemical stability, which is in the oral cavity is constantly flushed with a wide variety of fluids.
Der Erfindung liegt demgemäß die Aufgabe zugrunde, ein Verfahren zur Herstellung von geformten transluzenten Lithiumdisilikat-Glaskeramik-Produkten zur Verfügung zu stellen, die eine hohe chemische Stabilität, eine geringe Fehlstellendichte sowie eine hohe Transluzenz bei gleichzeitig guten mechanischen Eigenschaften haben und bei Weiterverarbeitung durch Verpressen im plastischen Zustand eine nur geringe Reaktion mit der eingesetzten Einbettmasse zeigen, und die Glaskeramik-Produkte auch in Form von Rohlingen mit geringem Kristallisationsgrad hergestellt werden können, die in einfacher Weise durch maschinelle Bearbeitung, wie spanende Verfahren, in gewünschter Weise geformt und durch anschließende Wärmebehandlung zu einem hochfesten Glaskeramik-Produkt umgewandelt werden können.The invention is accordingly based on the object of a method for the production of shaped translucent lithium disilicate glass ceramic products to provide that a high chemical stability, a low density of defects and a high translucency with good mechanical properties have and during further processing by pressing in plastic state a little reaction with the inserted Investment material show, and the glass ceramic products also in Formed blanks with a low degree of crystallization that can be easily machined, like machining processes, shaped in the desired manner and by subsequent heat treatment to a high strength Glass ceramic product can be converted.
Diese Aufgabe wird durch das Verfahren zur Herstellung von geformten transluzenten Lithiumdisilikat-Glaskeramik-Produkten nach den Ansprüchen 1 bis 12 gelöst.This task is accomplished through the process of manufacturing shaped translucent lithium disilicate glass ceramic products solved according to claims 1 to 12.
Gegenstand der Erfindung sind ebenfalls die geformten Glaskeramik-Produkte nach den Ansprüchen 13 bis 15, die Verwendung nach Anspruch 16 sowie die geformten Dentalprodukte nach den Ansprüchen 17 bis 19.The invention also relates to the shaped glass ceramic products according to claims 13 to 15, the use according to Claim 16 and the shaped dental products according to the claims 17 to 19.
Das erfindungsgemäße Verfahren zur Herstellung von geformten
transluzenten Lithiumdisilikat-Glaskeramik-Produkten zeichnet
sich dadurch aus, daß man
In Verfahrensschritt (a) wird eine Schmelze eines Ausgangsglases erzeugt, wozu geeignete Ausgangsmaterialien, wie z.B. Carbonate, Oxide, Phosphate und Fluoride, innig miteinander vermischt und auf Temperaturen von insbesondere 1200 bis 1600°C erwärmt werden. Zur Erzielung einer besonders hohen Homogenität kann die erzeugte Glasschmelze unter Bildung eines Glasgranulates in Wasser eingegossen und das erhaltene Glasgranulat erneut bei Temperaturen von insbesondere 1200 bis 1600°C während 1 bis 4 Stunden erschmolzen werden. In process step (a) there is a melt of an initial glass generated, for which suitable starting materials, e.g. Carbonates, Oxides, phosphates and fluorides, intimately mixed and heated to temperatures of in particular 1200 to 1600 ° C. become. To achieve a particularly high degree of homogeneity, the produced glass melt to form a glass granulate in Poured water and the glass granules obtained again Temperatures of in particular 1200 to 1600 ° C for 1 to 4 Hours are melted.
Die Schmelze der Ausgangsglases enthält vorzugsweise mindestens
eine der folgenden weiteren Komponenten:
Erstaunlicherweise wurde festgestellt, daß der zusätzliche Einbau von ZrO2 zu einer Erhöhung der Transluzenz führte, obwohl der gegenteilige Effekt in der konventionellen Glaskeramik gemäß EP-B-536 479 beobachtet wurde.Surprisingly, it was found that the additional incorporation of ZrO 2 led to an increase in translucency, although the opposite effect was observed in the conventional glass ceramic according to EP-B-536 479.
Für die Mengen der einzelnen Komponenten existieren, sofern nicht
anders angegeben, unabhängig voneinander wählbare Bereiche, die
wie folgt sind:
Als Farbkomponente oder Fluoreszenzkomponente können z.B. Oxide
von f-Elementen verwendet werden. Bevorzugt wird mindestens eine
der folgenden Verbindungen eingesetzt.
Die speziellen im erfindungsgemäßen Verfahren als Farb- oder Fluoreszenzkomponente einsetzbaren Oxide gewährleisten eine einfache Anpassung der Farbe des Glaskeramik-Produktes an den jeweiligen Anwendungszweck. Dies ist von besonderer Bedeutung, wenn die Glaskeramik-Produkte als Dentalprodukte eingesetzt werden sollen, deren Farbe an die des natürlichen Zahnmaterials des jeweiligen Patienten speziell angepaßt werden muß. Das mit diesen speziellen Oxiden erzielbare Farbspektrum reicht von sehr hellen Tönen bis zu stark grau-braunen Tönen z.B. bei devitalen Zahnstümpfen. Dabei wird durch etwaige vorhandene Fluoreszenzkomponenten die Fluoreszenz des natürlichen Zahnmaterials imitiert. Ein besonderer Vorteil der erfindungsgemäß eingesetzten Farb- und Fluoreszenzkomponenten ist, daß sie das Gefüge der erzeugten Glaskeramik-Produkte nicht in der Weise stören, daß inhomogene Materialien mit hoher Fehlstellendichte und hoher Porosität erzeugt werden. Dieses Problem tritt häufig bei Sinterkeramiken auf, deren Farbe durch Zugabe von Pigmenten verändert wird. Zur Vermeidung von Einbußen ihrer färbenden Wirkung werden diese Pigmente in der Regel erst vor Durchführung des bei relativ niedrigen Temperaturen durchgeführten Sintervorganges zugegeben, so daß sie stets als Kristalle oder Kristallite vorliegen, die zu Inhomogenitäten führen.The special in the process according to the invention as color or Fluorescence components that can be used ensure an easy adjustment of the color of the glass ceramic product to the respective application. This is of particular importance when the glass ceramic products are used as dental products should be whose color matches that of the natural tooth material of the respective patient must be specially adapted. That with The color spectrum that can be achieved with these special oxides ranges from very high light tones to strong gray-brown tones e.g. at devitalen Tooth stumps. This is due to any existing fluorescent components imitates the fluorescence of the natural tooth material. A particular advantage of the color and Fluorescence components is that they are the structure of the generated Glass ceramic products do not interfere in the way that inhomogeneous Materials with high defect density and high porosity be generated. This problem often occurs with sintered ceramics whose color is changed by adding pigments. For This will avoid loss of their coloring effect Pigments usually only before performing the at relative sintering process carried out at low temperatures, so that they are always present as crystals or crystallites that lead to inhomogeneities.
Neben den zuvor erwähnten Komponenten kann das Ausgangsglas auch noch Zusatzkomponenten enthalten, wofür insbesondere B2O3, Na2O, BaO, F und/oder SrO in Frage kommen.In addition to the components mentioned above, the starting glass can also contain additional components, for which B 2 O 3 , Na 2 O, BaO, F and / or SrO are particularly suitable.
Bevorzugt besteht die Schmelze des Ausgangsglases aus den erwähnten Komponenten in den angegebenen Mengen.The melt of the starting glass preferably consists of the mentioned components in the specified amounts.
Weiter wird in Stufe (b) die Schmelze des Ausgangsglases in der gewünschten Weise geformt und abgekühlt. Dabei erfolgt das Formen insbesondere durch Eingießen der Schmelze in eine gewünschte Form. Es ist weiter möglich, daß nach dem Eingießen auch noch eine Verdichtung der Schmelze durch Druck erfolgt, um eine besonders gute Homogenität und genaue Abbildung zu erzielen. Dabei kann in der Weise vorgegangen werden, daß ein Glastropfen in die gewünschte Form eingebracht und anschließend durch Pressen verdichtet wird.Next in stage (b) is the melt of the starting glass in the molded and cooled as desired. This is where the molding takes place especially by pouring the melt into a desired one Shape. It is further possible that even after pouring the melt is compressed by a pressure to achieve particularly good homogeneity and accurate imaging. This can be done in such a way that a glass drop brought into the desired shape and then by pressing is compressed.
Die Abkühlung der Schmelze erfolgt insbesondere in kontrollierter Weise, um damit den mit schnellen Temperaturwechseln einhergehenden Spannungen im Gefüge und daraus möglicherweise resultierenden Rissen und Sprüngen vorzubeugen. In der Regel wird daher die Schmelze in vorgewärmte Formen eingegossen oder in einem Ofen langsam abgekühlt. The melt is cooled in a controlled manner Way to deal with rapid temperature changes Tensions in the structure and possibly resulting from it To prevent cracks and cracks. As a rule, therefore Melt poured into preheated molds or in an oven cooled slowly.
Schließlich wird in Stufe (c) das gebildete geformte Glas-Produkt mindestens einer Wärmebehandlung unterzogen, um auf diese Weise dessen Kristallisation zu bewirken. Nach Abschluß dieser Verfahrensstufe wird ein als Rohling vorliegendes geformtes Glaskeramik-Produkt erhalten. Dieser Rohling hat üblicherweise die Form eines kleinen Zylinders oder eines rechteckigen Blockes. Die Wärmebehandlung erfolgt vorzugsweise bei einer Temperatur von weniger als 1000 und insbesondere weniger als 900 °C. Dabei wird das geformte Glasprodukt vorzugsweise in einen bereits auf die genannte Temperatur aufgeheizten Ofen eingebracht. Im Gegensatz zu konventionellen Materialien ist es nicht erforderlich, eine langsame Aufheizgeschwindigkeit zu wählen, um Spannungen auszuschließen. Für dieses vorteilhafte Verhalten ist offenbar die spezielle Zusammensetzung und Herstellungsweise des erfindungsgemäßen Materials verantwortlich.Finally, in step (c) the molded glass product formed subjected to at least one heat treatment in this way to cause its crystallization. After completing this The process step is a molded one that is present as a blank Glass ceramic product received. This blank usually has the shape of a small cylinder or a rectangular block. The heat treatment is preferably carried out at a temperature of less than 1000 and especially less than 900 ° C. Doing so the molded glass product preferably into one already on the mentioned temperature heated furnace introduced. In contrast to conventional materials it is not necessary to use one slow heating rate to choose to voltages to exclude. For this beneficial behavior is obvious the special composition and production method of the invention Materials responsible.
Der Kristallisationsgrad und die Kristallgröße in diesem Glaskeramik-Rohling kann durch die Art der gewählten Wärmebehandlung in einem sehr breiten Bereich variiert werden. So ist es einerseits möglich, ein Glas mit lediglich Keimen oder sehr kleinen Kristallen im Submikron-Bereich zu erzeugen, was somit die einfachste Form einer Glaskeramik darstellt, oder andererseits eine vollständig kristallisierte Glaskeramik zu bilden. In jedem Fall läuft der Keramisierungsprozeß über den Mechanismus der Volumenkristallisation ab, und für die Bildung von im Gefüge feinverteilten Kristallen spielen in dem eingesetzten Ausgangsglas vorhandene Volumenkeimbildner, wie z.B. P2O5, eine wesentliche Rolle.The degree of crystallization and the crystal size in this glass ceramic blank can be varied within a very wide range by the type of heat treatment selected. On the one hand, it is possible to produce a glass with only germs or very small crystals in the submicron range, which is the simplest form of a glass ceramic, or on the other hand to form a completely crystallized glass ceramic. In any case, the ceramization process takes place via the mechanism of volume crystallization, and volume nucleating agents, such as, for example, P 2 O 5 , play an important role in the formation of crystals which are finely distributed in the structure.
Zur Erzeugung des endgültigen Glaskeramik-Produktes, wie z.B. einer dentalen Brücke oder einer dentalen Krone, bestehen insbesondere die folgenden zwei Möglichkeiten (d1) und (d2).To produce the final glass ceramic product, e.g. a dental bridge or a dental crown in particular the following two options (d1) and (d2).
Zum einen kann in Stufe (d1) das als Rohling vorliegende Glaskeramik-Produkt bei einer Temperatur von 700 bis 1200 °C und durch Anwendung von Druck, insbesondere von 8 bis 40 bar, zu einem Glaskeramik-Produkt gewünschter Geometrie plastisch verformt werden. Für diesen Formgebungsschritt ist es bevorzugt, das in der EP-A-231 773 beschriebene Verfahren zur Herstellung von Zahnersatzteilen sowie den dort ebenfalls offenbarten Preßofen zu benutzen. Bei diesem Verfahren wird der Rohling im plastischen Zustand in einen dem gewünschten geformten Dentalprodukt, wie z.B. Kronen, entsprechenden Formhohlraum unter Anwendung von Wärme und Druck eingepreßt. Der hierfür insbesondere eingesetzte Preßofen wird als Empress®-Ofen von der Ivoclar AG, Liechtenstein, vertrieben.On the one hand, in step (d1), the present as a blank Glass ceramic product at a temperature of 700 to 1200 ° C and by applying pressure, in particular from 8 to 40 bar a glass ceramic product of the desired geometry be deformed. For this shaping step it is preferred the production process described in EP-A-231 773 of dental prostheses as well as those also disclosed there Press furnace to use. In this process, the blank in plastic state into a desired dental product, such as. Crowns, corresponding mold cavity under Pressed in using heat and pressure. The one in particular Press furnace used is from the Ivoclar AG, Liechtenstein.
Es hat sich gezeigt, daß herkömmliche Lithiumdisilikat-Glaskeramiken bei der Weiterverarbeitung zu Glaskeramik-Produkten durch plastische Verformung eine unangemessen hohe Reaktion mit der verwendeten Einbettmasse zeigen, in nur ungenügendem Maße fließen oder unkontrolliertes Kristallwachstum zeigen. Diese Nachteile werden bei dem erfindungsgemäßen Verfahren durch die Verwendung von La2O3 und gegebenenfalls Al2O3 in den angegebenen Mengen im Ausgangsglas vermieden. Hierdurch kann das als Rohling vorliegende Glaskeramik-Produkt durch das Verpressen im plastischen Zustand in vorteilhafter Weise zu einem Glaskeramik-Produkt gewünschter Geometrie, insbesondere einem Dentalprodukt, wie einer Dentalrestauration, verarbeitet werden.It has been shown that conventional lithium disilicate glass ceramics show an inappropriately high reaction with the investment material used during further processing to glass ceramic products, flow to an insufficient extent or show uncontrolled crystal growth. These disadvantages are avoided in the process according to the invention by using La 2 O 3 and optionally Al 2 O 3 in the amounts stated in the starting glass. As a result, the glass ceramic product, which is in the form of a blank, can advantageously be processed by pressing in the plastic state into a glass ceramic product of the desired geometry, in particular a dental product, such as a dental restoration.
Weiter ist es möglich, das als Rohling vorliegende Glaskeramik-Produkt in Stufe (d2) durch spanende Bearbeitung, insbesondere CAD/CAM-gestützte Fräsgeräte, zu einem Glaskeramik-Produkt gewünschter Geometrie zu verarbeiten. Damit ist eine sogenannte "chair-side" Behandlung für den Zahnarzt möglich. Bei Durchführung dieser Weiterverarbeitungsvariante wird insbesondere ein Glaskeramik-Rohling eingesetzt, der noch nicht vollständig kristallisiert ist, sondern z.B. lediglich als keimhaltiger Glas-Rohling oder Glaskeramikrohling mit sehr kleinen Kristallen vorliegt. Derartige noch nicht vollständig kristallisierte Glaskeramik-Rohlinge zeigen den besonderen Vorteil, daß sie in deutlicher einfacherer Weise als herkömmliche Glaskeramiken maschinell zu dem fertigen Glaskeramik-Produkt gewünschter Geometrie verarbeitet werden können. Zur Herstellung eines Glaskeramik-Rohlings, bei dem die Glasmatrix lediglich Keime oder sehr kleine Kristallite enthält, hat es sich als besonders vorteilhaft erwiesen, die in Stufe (c) durchgeführte Wärmebehandlung bei einer Temperatur von 400 bis 900 °C durchzuführen. In jedem Fall kann der Kristallinitätsgrad des eingesetzten Glaskeramik-Rohlings an die Art der gewünschten spanenden Bearbeitung angepaßt werden, um diese möglichst einfach durchführen zu können.It is also possible to use the glass ceramic product as a blank in stage (d2) by machining, in particular CAD / CAM-based milling devices, to a glass ceramic product to process the desired geometry. So that's a so-called "Chair-side" treatment for the dentist possible. When performing this further processing variant is in particular a Glass ceramic blank used, which is not yet complete is crystallized, but e.g. only as a germ-containing glass blank or glass ceramic blank with very small crystals is present. Such has not yet fully crystallized Glass ceramic blanks have the particular advantage that they are in much easier than conventional glass ceramics desired by machine to the finished glass ceramic product Geometry can be processed. To make a Glass ceramic blanks in which the glass matrix is only germs or contains very small crystallites, it has turned out to be special proved to be advantageous, the heat treatment carried out in step (c) to be carried out at a temperature of 400 to 900 ° C. In in any case, the degree of crystallinity used Glass ceramic blanks to the type of cutting desired Editing can be adjusted to make this as easy as possible to be able to.
Nach der anschließenden spanenden Bearbeitung in Stufe (d2) wird das erhaltene geformte Glaskeramik-Produkt dann mindestens einer weiteren Wärmebehandlung, insbesondere bei 700 bis 900 °C, unterzogen, um eine weitere Kristallisation und damit Verfestigung des Glaskeramik-Produktes zu erzielen. Durch diese weitere Wärmebehandlung werden die Bruchfestigkeit, die Farbe und die Transluzenz verbessert.After the subsequent machining in stage (d2) the molded glass ceramic product obtained then at least one further heat treatment, especially at 700 to 900 ° C, subjected to further crystallization and thus solidification of the glass ceramic product. Through this further heat treatment are breaking strength, color and improves translucency.
Das nach der Weiterverarbeitung, insbesondere in den Stufen (d1) und (d2), vorliegende fertige Glaskeramik-Produkt gewünschter Geometrie kann schließlich noch mit einer Beschichtung versehen werden, was gerade bei dessen Einsatz im Dentalbereich vorteilhaft ist. Als Beschichtung kommen dabei insbesondere eine Keramik, eine Sinterkeramik, eine Glaskeramik, bevorzugt eine Apatit-Glaskeramik, ein Glas, eine Glasur und/oder ein Composit in Frage. Vorteilhaft sind solche Beschichtungen, die eine Sintertemperatur von 650 bis 950 °C und einen linearen thermischen Ausdehnungskoeffizient haben, welcher kleiner ist als der des zu beschichtenden Glaskeramik-Produktes. Besonders vorteilhaft sind Beschichtungen, deren linearer thermischer Ausdehnungskoeffizient nicht mehr als ± 3,0 × 10-6 K-1 von dem des Substrats abweicht.The finished glass ceramic product of the desired geometry present after further processing, in particular in stages (d1) and (d2), can finally be provided with a coating, which is particularly advantageous when it is used in the dental field. A ceramic, a sintered ceramic, a glass ceramic, preferably an apatite glass ceramic, a glass, a glaze and / or a composite are particularly suitable as coatings. Coatings which have a sintering temperature of 650 to 950 ° C. and a linear thermal expansion coefficient which is smaller than that of the glass ceramic product to be coated are advantageous. Coatings whose linear thermal expansion coefficient does not differ by more than ± 3.0 × 10 -6 K -1 from that of the substrate are particularly advantageous.
Das Aufbringen einer Beschichtung erfolgt insbesondere durch Aufsinterung. Während dieses Sintervorganges wird das die Lithiumdisilikat-Glaskeramik enthaltende Glaskeramik-Produkt allerdings in einen Temperaturbereich gebracht, der oberhalb des Transformationspunktes der Restglasmatrix der Glaskeramik liegt. Herkömmliche Lithiumdisilikat-Glaskeramiken werden dabei häufig in unerwünschter Weise deformiert, da sie eine zu geringe Temperaturstandfestigkeit haben. Das erfindungsgemäß hergestellte Glaskeramik-Produkt hat jedoch eine ausgezeichnete Temperaturstandfestigkeit, wofür insbesondere der Gehalt an La2O3 und gegebenenfalls Al2O3 in den angegebenen Mengen verantwortlich ist.A coating is applied in particular by sintering. During this sintering process, however, the glass ceramic product containing the lithium disilicate glass ceramic is brought into a temperature range which lies above the transformation point of the residual glass matrix of the glass ceramic. Conventional lithium disilicate glass ceramics are often deformed in an undesirable manner because they have insufficient temperature stability. However, the glass ceramic product produced according to the invention has an excellent temperature stability, for which the content of La 2 O 3 and optionally Al 2 O 3 in the stated amounts is particularly responsible.
Die erfindungsgemäß hergestellten Glaskeramik-Produkte sind aufgrund ihrer Eigenschaften besonders zum Einsatz als Dentalprodukte oder Bestandteile von diesen geeignet. So haben bevorzugte Glaskeramik-Produkte eine 3-Punkt-Biegefestigkeit von mehr als 400 MPa; wenn sie nach Verfahrensvariante (d1) hergestellt werden, und mehr als 250 MPa, wenn sie nach Verfahrensvariante (d2) hergestellt werden. Das zur Ermittlung der 3-Punkt-Biegefestigkeit benutzte Verfahren ist in den Beispielen erläutert.The glass ceramic products produced according to the invention are due to their properties, especially for use as dental products or components of these are suitable. Have so preferred glass ceramic products have a 3-point bending strength more than 400 MPa; if it is produced according to process variant (d1) be, and more than 250 MPa if according to process variant (d2) can be produced. That to determine the 3-point bending strength The procedure used is in the examples explained.
Weiter haben die erfindungsgemäßen Glaskeramik-Produkte eine mit
der des natürlichen Zahnes vergleichbare Transluzenz. Zur
Quantifizierung der Transluzenz wurde nach dem in den Beispielen
beschriebenen Meßverfahren der CR-Wert bestimmt. Der CR-Wert,
auch als Kontrastverhältnis bezeichnet, gibt das Verhältnis der
Lichtreflexion eines Probekörpers der Glaskeramik auf schwarzem
Hintergrund zu der Messung der Lichtreflexion eines Probekörpers
auf weißem Hintergrund an und dient somit als Maß für die
Transluzenz eines Materials. Der CR-Wert ist durch die folgende
Formel definiert:
- CR
- = Kontrastverhältnis,
- Yb
- = Lichtreflexion des Probekörpers auf schwarzem Hintergrund, und
- Yw
- = Lichtreflexion des Probekörpers auf weißem Hintergrund.
- CR
- = Contrast ratio,
- Y b
- = Light reflection of the test specimen on a black background, and
- Y w
- = Light reflection of the test specimen on white background.
Der CR-Wert liegt stets im Bereich von 0 bis 1, wobei CR = 0 für eine Opazität von 0 % und demnach ein vollständiges transluzentes Material und CR = 1 für eine Opazität von 100 % und demnach ein vollständig opakes, d.h. lichtundurchlässiges Material steht.The CR value is always in the range from 0 to 1, with CR = 0 for an opacity of 0% and therefore a complete translucent Material and CR = 1 for an opacity of 100% and therefore one completely opaque, i.e. opaque material.
Das erfindungsgemäße Glaskeramik-Produkt hat üblicherweise einen CR-Wert von 0,05 bis 0,9 und bevorzugt von 0,1 bis 0,75, jeweils gmessen bei einer Probendicke von 1,2 mm.The glass ceramic product according to the invention usually has one CR value from 0.05 to 0.9 and preferably from 0.1 to 0.75, each gmeasured with a sample thickness of 1.2 mm.
Auch haben Untersuchungen des erfindungsgemäßen Glaskeramik-Produktes gezeigt, daß dieses ein sehr homogenes Gefüge mit gleichmäßig verteilten feinen Kristallen aufweist. Es wird angenommen, daß dieses spezielle Gefüge durch die besondere Zusammensetzung des eingesetzten Ausgangsglases sowie das Formen, insbesondere Gießen von Massivglas-Rohlingen in Stufe (b) hervorgerufen wird und für die besonders hohe Festigkeit des schließlich erhaltenen Glaskeramik-Produktes verantwortlich ist.Also have investigations of the glass ceramic product according to the invention shown that this has a very homogeneous structure evenly distributed fine crystals. It will assumed that this special structure through the special Composition of the starting glass used and shaping, in particular casting of solid glass blanks in stage (b) is caused and for the particularly high strength of the ultimately obtained glass ceramic product is responsible.
Es ist zudem überraschend, daß die Farbe, Transluzenz und Fluoreszenz des erfindungsgemäßen Glaskeramik-Produktes an die eines natürlichen Zahnes angepaßt werden kann, ohne daß die dabei eingesetzten Farb- und Fluoreszenzkomponenten die Festigkeit und Zähigkeit der Glaskeramik nachteilig beeinflussen würden. Im Gegensatz dazu ist bei Glaskeramiken auf Leucit-Basis bekannt, daß durch solche Zusätze die Kristallisation stark beeinflußt und die Festigkeit häufig sehr verringert wird. So ist es bei Sinterkeramiken bekannt, daß die in ihnen vielfach eingesetzten Pigmente zu einer recht hohen Fehlstellendichte und einer Porenbildung in der Glaskeramik führen, was wiederum deren Eigenschaften verschlechtert.It is also surprising that the color, translucency and Fluorescence of the glass ceramic product according to the invention a natural tooth can be adjusted without the color and fluorescence components used the strength and Would adversely affect toughness of the glass ceramic. in the In contrast, it is known for glass ceramics based on leucite that that the crystallization is strongly influenced by such additives and the strength is often greatly reduced. So it is with Sintered ceramics are known to be widely used in them Pigments to a quite high defect density and one Pore formation in the glass ceramic lead, which in turn cause their Properties deteriorated.
Schließlich zeichnet sich das erfindungsgemäße Glaskeramik-Produkt durch eine ausgezeichnete Säurebeständigkeit aus, die vorzugsweise weniger als 100 µg/cm2 Masseverlust beträgt. Dieser Masseverlust wurde nach dem in den Beispielen erläuterten Verfahren bestimmt, bei dem die Glaskeramik über einen bestimmten Zeitraum mit wäßriger Essigsäure behandelt wird, und der nach der Behandlung festgestellte Masseverlust als Maß für die Säurebeständigkeit dient.Finally, the glass ceramic product according to the invention is distinguished by excellent acid resistance, which is preferably less than 100 μg / cm 2 loss in mass. This loss of mass was determined according to the method explained in the examples, in which the glass ceramic is treated with aqueous acetic acid for a certain period of time, and the loss of mass found after the treatment serves as a measure of the acid resistance.
Bevorzugte geformte Dentalprodukte, die das erfindungsgemäße Glaskeramik-Produkt aufweisen, sind Dentalrestaurationen, wie z.B. ein Inlay, ein Onlay, eine Brücke, ein Stiftaufbau, eine Verblendung, ein Veneer, eine Facette, eine Krone oder eine Teilkrone.Preferred molded dental products that the invention Glass ceramic product, dental restorations are like e.g. an inlay, an onlay, a bridge, a pen structure, an Veneer, a veneer, a facet, a crown or a Partial crown.
Weiter sind solche geformten Dentalprodukte bevorzugt, die als Rohlinge vorliegen, d.h. bei denen noch eine Weiterverarbeitung zu dem endgültigen Dentalprodukt, z.B. nach den Stufen (d1) und (d2) erfolgt. Solche Rohlinge können in verschiedenen dem jeweiligen Weiterverarbeitungsverfahren angepaßten Formen vorliegen, wie z.B. kleine Zylinder oder rechteckige Blöcke.Furthermore, such shaped dental products are preferred which are used as There are blanks, i.e. where there is still further processing to the final dental product, e.g. after steps (d1) and (d2) takes place. Such blanks can be used in different ways there are forms adapted to the respective further processing methods, such as. small cylinders or rectangular blocks.
Die Erfindung wird im folgenden anhand von Beispielen näher erläutert.The invention is illustrated below with the aid of examples explained.
Es wurden insgesamt 20 verschiedene erfindungsgemäße Glaskeramik-Produkte mit der in Tabelle I angegebenen chemischen Zusammensetzungen hergestellt, indem die Stufen (a) bis (c) des beschriebenen Verfahrens durchgeführt wurden. A total of 20 different glass ceramic products according to the invention were produced with the chemical compositions given in Table I by carrying out steps (a) to (c) of the process described.
Dieses Beispiel beschreibt die Herstellung eines erfindungsgemäßen Glaskeramik-Rohlings, welcher zur Herstellung eines individuell formbaren vollkeramischen Dentalproduktes, wie z.B. eine Krone oder eine mehrgliedrige Brücke, dienen kann. Auf das Dentalprodukt kann dann zusätzlich eine angepaßte Dentalsinterkeramik aufgebrannt werden.This example describes the preparation of an inventive Glass ceramic blank, which is used to manufacture a individually formable all-ceramic dental product, e.g. a crown or a multi-unit bridge. On the Dental product can then also have an adapted dental sintered ceramic be burned.
Zunächst wurde ein Ausgangsglas mit der in der Tabelle I für Beispiel 14 angegebenen chemischen Zusammensetzung hergestellt. Dazu wurde ein Gemenge aus entsprechenden Oxiden, Carbonaten und Phosphaten in einer Kugelmühle gemischt und in einem Platin/Rhodium-Tiegel bei einer Temperatur von 1500 °C und einer Homogenisierungszeit von 2 Stunden erschmolzen. Die erhaltene Glasschmelze wurde durch Eingießen in Wasser granuliert, und die gebildete Glasfritte wurde getrocknet. Dann wurde die Glasfritte erneut in eine Kugelmühle aufgemahlen und nochmals bei 1500 °C und einer Homogenisierungszeit von 2 Stunden geschmolzen. Die erhaltene homogene, transparente und leicht gelb gefärbte Schmelze wurde anschließend in eine bei 500 °C vorgewärmte Stahlform zu zylindrischen Stäben gegossen, die in einem Ofen kontrolliert von 500 °C langsam auf Raumtemperatur abgekühlt wurden. Die erhaltenen Glasstäbe wurden zu Proben von 2 g, 3 g und 4 g gesägt und dann 30 Minuten lang bei 870 °C wärmebehandelt, um die entsprechenden Glaskeramik-Rohlinge zu bilden. Dabei wurden die abgekühlten Glasstäbe direkt in den auf 870 °C vorgeheizten Ofen gelegt. Eine langsame Aufheizgeschwindigkeit war nicht erforderlich. First, a starting glass with the in Table I for Example 14 chemical composition prepared. For this purpose, a mixture of appropriate oxides, carbonates and Phosphates mixed in a ball mill and in a platinum / rhodium crucible at a temperature of 1500 ° C and one Homogenization time of 2 hours melted. The received Glass melt was granulated by pouring it into water, and the Glass frit formed was dried. Then the glass frit ground again in a ball mill and again at 1500 ° C and a homogenization time of 2 hours melted. The obtained homogeneous, transparent and slightly yellow colored The melt was then preheated to 500 ° C Steel mold cast into cylindrical bars, which are in an oven cooled slowly from room temperature to 500 ° C were. The glass rods obtained became samples of 2 g, 3 g and sawed 4 g and then heat treated at 870 ° C for 30 minutes, to form the corresponding glass ceramic blanks. Here the cooled glass rods were directly in the to 870 ° C preheated oven. A slow heating rate was not required.
Die erhaltenen Glaskeramik-Rohlinge wiesen vergleichbare optische Eigenschaften, wie z.B. Transluzenz, Färbung und Trübung, wie übliche dentalkeramische Verkaufsprodukte auf, z.B. IPS Empress-Rohlinge von Ivoclar AG, Liechtenstein.The glass ceramic blanks obtained had comparable optical Properties such as Translucency, staining and turbidity, such as conventional dental ceramic sales products, e.g. IPS Empress blanks by Ivoclar AG, Liechtenstein.
Zur Bestimmung der 3-Punkt-Biegefestigkeit wurden aus den Glaskeramik-Rohlingen Stäbe als Prüfkörper gemäß ISO Dentalnorm 6872/1995 gefertigt. Die Ermittlung der 3-Punkt-Biegefestigkeit erfolgte dann ebenfalls gemäß ISO 6872-1995 E "Dental Ceramic" mit einer Vorschubgeschwindigkeit der Lastaufbringung von 0,5 mm/min und einer Stützweite des Prüfmittels von 15 mm. Die unter diesen Bedingungen ermittelte Biegefestigkeit betrug 408 ± 63 MPa.To determine the 3-point bending strength, the Glass ceramic blanks rods as test specimens according to ISO dental standard 6872/1995 manufactured. The determination of the 3-point bending strength was then also carried out according to ISO 6872-1995 E "Dental Ceramic" at a feed rate of load application of 0.5 mm / min and a span of the test equipment of 15 mm. The flexural strength determined under these conditions was 408 ± 63 MPa.
Die erhaltenen Glaskeramik-Rohlinge wurden unter Verwendung des Heißpreßverfahrens gemäß EP-A-231 773 und des dort ebenfalls beschriebenen Preßofens unter Vakuum im viskosen Zustand in die für die jeweiligen Test gewünschte Probengeometrie verpreßt. Dabei betrugen die Bereitschaftstemperatur des Preßofens 800 °C, die Heizrate bis zur Preßtemperatur 60 °C/min, die Preßtemperatur 910 °C, die Haltezeit bei der Preßtemperatur 15 Minuten und die Preßdruckanzeige 5 bar. Nach dem Preßvorgang wurde die Preßform an der Luft abgekühlt, und die erhaltenen geformten Glaskeramik-Produkte wurden durch Sandstrahlen mit Al2O3-Pulver und Glasperlen entformt. Die Produkte hatten folgende Eigenschaften. The glass ceramic blanks obtained were pressed into the sample geometry desired for the respective test under vacuum in the viscous state using the hot pressing method according to EP-A-231 773 and the press furnace likewise described there. The standby temperature of the press furnace was 800 ° C, the heating rate up to the press temperature 60 ° C / min, the press temperature 910 ° C, the holding time at the press temperature 15 minutes and the press pressure display 5 bar. After the pressing process, the mold was cooled in air and the shaped glass ceramic products obtained were removed from the mold by sandblasting with Al 2 O 3 powder and glass beads. The products had the following properties.
Zur Quantifizierung der Transluzenz der Glaskeramik-Produkte wurde der CR-Wert nach dem Meßverfahren der British Standards Institution ermittelt, welches in der Prüfnorm von Dentalkeramik "BS 5612: 1978" beschrieben ist.For quantifying the translucency of glass ceramic products the CR value was measured using the British Standards measurement method Institution determines which in the test standard of dental ceramics "BS 5612: 1978" is described.
Hierzu wurden 5 Prüfkörper mit einem Durchmesser von 16 mm und einer Probendicke von 1,4 mm hergestellt. Die Prüfkörper wurden mit nassem SiC-Pulver, Körnung 320, beschliffen, um die gewünschte Oberflächengüte zu erhalten (Oberflächenrauhigkeit Ra = 0,8 µm bis 1,6 µm). Dabei ist es wichtig, daß die Planparallelität der gegenüberliegenden Seiten eine Toleranz von ± 0,01 mm nicht überschreitet, da das Meßergebnis in hohem Maße von der Schichtstärke abhängt. Die endgültige Probenhöhe/-dicke betrug 1,2 ± 0,025 mm.For this purpose, 5 test specimens with a diameter of 16 mm and a sample thickness of 1.4 mm. The test specimens were with wet SiC powder, grit 320, ground to the desired Maintain surface quality (surface roughness Ra = 0.8 µm to 1.6 µm). It is important that the plane parallelism of the opposite sides a tolerance of Does not exceed ± 0.01 mm, since the measurement result is high depends on the layer thickness. The final sample height / thickness was 1.2 ± 0.025 mm.
Die Prüfkörper wurden in einem Farbmeßinstrument Minolta-CR300
in die vorgesehene Meßöffnung gelegt, und die Remission von jedem
der 5 Prüfkörper wurde mit einer Blende von 10 mm gemessen. Bei
der Messung dürfen die Proben nicht in optischen Kontakt mit dem
Hintergrund sein, was gegebenenfalls durch Aufgabe eines Tropfens
Glycerin auf den Hintergrund verhindert wurde.
Aus den ermittelten Werten Yb und Yw wurde dann der Kontrastwert CR = Yb/Yw berechnet, und er betrug 0,63. The contrast value CR = Y b / Y w was then calculated from the determined values Y b and Y w and was 0.63.
Infolge der transluzenten Eigenschaften war dieses Glaskeramik-Produkt als vollkeramisches Dentalprodukt geeignet, das optisch den Vorgaben eines natürlichen Zahnes entspricht. Durch den Einsatz von glasfärbenden Oxiden im Ausgangsglas war das heißgepreßte Glaskeramik-Produkt zahnfarben getönt, wobei die Farbintensität und -tönung durch die Konzentration der färbenden Oxide eingestellt werden konnte.Due to the translucent properties, this glass ceramic product was suitable as an all-ceramic dental product, the optically corresponds to the specifications of a natural tooth. By the That was the use of glass-coloring oxides in the source glass hot-pressed glass-ceramic product tinted tooth-colored, the Color intensity and tint due to the concentration of the coloring Oxides could be adjusted.
Auf das als Gerüstmaterial einsetzbare transluzente Glaskeramik-Produkt konnte eine transluzente bis transparente Dentalsinterglaskeramik mit einem Ausdehnungskoeffizienten von 9,5 × 10-6 K-1 (100 bis 400 °C) als Beschichtung aufgebracht werden. Dabei wurde die Dentalsinterglaskeramik schichtweise auf das Glaskeramik-Produkt unter Vakuum bei 760 °C aufgesintert, was zu transluzenten vollkeramischen Dentalrestaurationen führte, die den hohen ästhetischen Anforderungen an derartige Produkte genügen.A translucent to transparent dental sintered glass ceramic with an expansion coefficient of 9.5 × 10 -6 K -1 (100 to 400 ° C.) could be applied as a coating on the translucent glass ceramic product that can be used as the framework material. The dental sintered glass ceramic was sintered in layers onto the glass ceramic product under vacuum at 760 ° C, which led to translucent all-ceramic dental restorations that meet the high aesthetic requirements for such products.
Die 3-Punkt-Biegefestigkeit wurde an heißgepreßten Glaskeramik-Stäben entsprechend dem oben für die Rohlinge benutzten Verfahren bestimmt. Dabei wurde eine 3-Punkt-Biegefestigkeit von 450 ± 85 MPa ermittelt.The 3-point bending strength was measured on hot-pressed glass ceramic rods according to the procedure used above for the blanks certainly. A 3-point bending strength of 450 ± 85 MPa determined.
Hierfür wurden zylindrische Glaskeramik-Proben mit einem Durchmesser von 6 mm und einer Länge von 20 mm heißgepreßt. Der im Temperaturbereich von 100 bis 500 °C für diese Proben bestimmte Ausdehnungskoeffizient betrug 10,8 × 10-6 K-1. For this purpose, cylindrical glass ceramic samples with a diameter of 6 mm and a length of 20 mm were hot pressed. The coefficient of expansion determined for these samples in the temperature range from 100 to 500 ° C. was 10.8 × 10 -6 K -1 .
Hierzu wurden Glaskeramik-Stäbe mit den Maßen 20 × 4,4 × 1,4 mm3 heißgepreßt und anschließend mit SiC-Naßschleifpapier (1000er Körnung) allseitig überschliffen. Mit einer Diamanttrennscheibe (0,2 mm Dicke) wurden die Proben einseitig bis zur Mitte auf eine Tiefe von 2,2 mm gekerbt und anschließend nach DIN 51 109 bei einer äußeren Stützweite von 15 mm und einer Vorschubgeschwindigkeit der Lastaufbringung von 0,5 mm/min mittels 4-Punkt-Biegeanordnung geprüft. Der ermittelte KIC-Wert betrug 3,0 ± 0,3 MPa √m.For this purpose, glass ceramic rods with the dimensions 20 × 4.4 × 1.4 mm 3 were hot-pressed and then ground on all sides with SiC wet abrasive paper (1000 grit). With a diamond cutting disc (0.2 mm thick), the samples were notched on one side up to the middle to a depth of 2.2 mm and then according to DIN 51 109 with an outer span of 15 mm and a feed rate of load application of 0.5 mm / min checked using a 4-point bending arrangement. The K IC value determined was 3.0 ± 0.3 MPa √m.
Hierzu wurden scheibenförmige Glaskeramik-Proben mit einem Durchmesser von 15 mm und einer Dicke von 1,5 mm heißgepreßt und anschließend mit SiC-Naßschleifpapier (1000er Körnung) allseitig überschliffen. Der gemäß ISO 6872-1995 E "Dental Ceramic" bestimmte flächenbezogene Masseverlust dieser Proben wurde nach 16-stündiger Lagerung in 4 vol.-%iger wäßriger Essigsäurelösung bestimmt. Der Wert betrug 36 µg/cm2 und lag deutlich unter dem Normwert für Dentalkeramiken von 2000 µg/cm2.For this purpose, disk-shaped glass ceramic samples with a diameter of 15 mm and a thickness of 1.5 mm were hot pressed and then ground on all sides with SiC wet sanding paper (1000 grit). The area-related mass loss of these samples, determined in accordance with ISO 6872-1995 E “Dental Ceramic”, was determined after 16 hours of storage in 4% by volume aqueous acetic acid solution. The value was 36 µg / cm 2 and was significantly below the standard value for dental ceramics of 2000 µg / cm 2 .
Dieses Beispiel beschreibt die Herstellung eines erfindungsgemäßen Glaskeramik-Rohlings, der durch spanende Bearbeitung und anschließend erneute Wärmebehandlung zu einem individuell geformten vollkeramischen Dentalprodukt, wie z.B. eine Krone oder eine mehrgliedrige Brücke, verarbeitet wird, auf das zusätzlich eine angepaßte transluzente bis transparente Dentalsinterkeramik aufgebrannt werden kann.This example describes the preparation of an inventive Glass ceramic blanks made by machining and then again heat treatment to an individual molded all-ceramic dental product, e.g. a crown or a multi-unit bridge that is processed on top of that an adapted translucent to transparent dental sintered ceramic can be burned.
Die Herstellung des Dentalproduktes erfolgte über ein CAD/CAM-Verfahren, wie z.B. CEREC 2®, von Siemens AG. The dental product was manufactured using a CAD / CAM process, such as. CEREC 2®, from Siemens AG.
Erst die nach der spanenden Bearbeitung durchgeführte Wärmebehandlung ergab das Dentalprodukt mit den hohen mechanischen Kennwerten, wie 3-Punkt-Biegefestigkeit, und den für ein dentalkeramisches Produkt geforderten guten optischen Eigenschaften.Only the heat treatment carried out after the machining resulted in the dental product with the high mechanical Characteristic values, such as 3-point bending strength, and that for one dental ceramic product required good optical properties.
Zunächst wurde ein Ausgangsglas mit der in der Tabelle I für Beispiel 7 angegebenen Zusammensetzung hergestellt. Dazu wurde ein Gemenge aus Oxiden, Carbonaten und Phosphaten in einer Kugelmühle gemischt und in einem Platin/Rhodium-Tiegel bei einer Temperatur von 1500 °C und einer Homogenisierungszeit von 2 Stunden erschmolzen. Die Glasschmelze wurde durch Eingießen in Wasser gefrittet, und die Fritte wurde nach Trocknung in einer Kugelmühle aufgemahlen und nochmals bei 1500 °C und einer Homogenisierungszeit von 2 Stunden geschmolzen. Die erhaltene homogene, transparente und leicht gelb gefärbte Schmelze wurde dann in eine auf 500 °C vorgewärmte Stahlform zu rechteckigen Blöcken mit den Dimensionen 65 × 20 × 16 mm3 gegossen und in einem Temperofen kontrolliert von 500 °C langsam auf Raumtemperatur abgekühlt. Die erhaltenen rechteckigen Glasblöcke wurden zu Proben mit den Maßen 18 × 14 × 20 mm3 gesägt. Diese Proben wurden dann 60 Minuten bei 650 °C wärmebehandelt. Dabei wurden die abgekühlen Glasblöcke direkt in den auf 650 °C aufgeheizten Ofen eingebracht. Die nach diesem ersten Temperschritt erhaltenen Glaskeramik-Rohlinge hatten die folgenden Eigenschaften.First, a starting glass with the composition given in Table I for Example 7 was produced. For this purpose, a mixture of oxides, carbonates and phosphates was mixed in a ball mill and melted in a platinum / rhodium crucible at a temperature of 1500 ° C. and a homogenization time of 2 hours. The glass melt was fritted by pouring it into water and, after drying, the frit was ground in a ball mill and melted again at 1500 ° C. and a homogenization time of 2 hours. The homogeneous, transparent and slightly yellow-colored melt obtained was then poured into a steel mold preheated to 500 ° C. to form rectangular blocks having the dimensions 65 × 20 × 16 mm 3 and slowly cooled from room temperature to 500 ° C. in a tempering furnace. The rectangular glass blocks obtained were sawn into samples measuring 18 × 14 × 20 mm 3 . These samples were then heat treated at 650 ° C for 60 minutes. The cooled glass blocks were placed directly in the oven heated to 650 ° C. The glass ceramic blanks obtained after this first tempering step had the following properties.
Die Glaskeramik-Rohlinge besaßen eine violett-weißliche Farbe. Sie hatten einen nach dem in Beispiel 21 beschriebenen Verfahren bestimmten CR-Wert von 0,36. The glass ceramic blanks had a violet-white color. They had one using the procedure described in Example 21 determined CR of 0.36.
Die gemäß Beispiel 21 für die Glaskeramik-Rohlinge bestimmte 3-Punkt-Biegefestigkeit betrug 171 ± 20 MPa.The 3-point bending strength determined according to Example 21 for the glass ceramic blanks was 171 ± 20 MPa.
Die einfach wärmebehandelten Glaskeramik-Rohlinge wurden mittels einer computergesteuerten Fräsmaschine zu dentalkeramischen Restaurationen, wie z.B. Kronen, verarbeitet. Aufgrund der relativ geringen Festigkeit und Zähigkeit der Glaskeramik-Rohlinge erwies sich die Verarbeitung als einfach durchführbar. Im Vergleich zu bekannten Fräskeramiken riefen sie einen geringeren Werkzeugverschleiß hervor, und es bildeten sich weniger Ausbrüche, was auf die feinere Struktur und Fehlstellenfreiheit zurückführbar ist.The simply heat-treated glass ceramic blanks were made using a computer-controlled milling machine for dental ceramics Restorations, e.g. Crowns, processed. Due to the relatively low strength and toughness of the glass ceramic blanks the processing proved to be easy to carry out. In comparison to known milling ceramics, they called you less tool wear, and it formed fewer breakouts, indicating the finer structure and freedom from defects is traceable.
Die gefräste dentale Restauration wurde dann einer weiteren Wärmebehandlung bei 760 °C während 1 h unterzogen. Diese Temperatur wurde gewählt, da bei ihr keine Gefahr einer Verformung des Gerüsts besteht. Diese zusätzliche Wärmebehandlung führte zu einer weitergehenden Kristallisation und damit Änderung der Eigenschaften der Restauration. Die erhaltene zweifach behandelte Glaskeramik hatte folgende Eigenschaften. The milled dental restoration was then another Subject to heat treatment at 760 ° C for 1 h. This Temperature was chosen because there was no risk of deformation of the scaffold. This additional heat treatment led to further crystallization and thus change the properties of the restoration. The received two Treated glass ceramics had the following properties.
Die Glaskeramik war transluzent und durch den Einsatz von glasfärbenden Oxiden im Ausgangsglas zahnfarben getönt.The glass ceramic was translucent and through the use of glass-staining oxides in toothpaste tinted in the starting glass.
Der für diese Glaskeramik gemäß Beispiel 21 bestimmte CR-Wert an zylindrischen Proben mit einem Durchmesser von 16 mm und einer Dicke von 1,2 mm betrug 0,23.The CR value determined for this glass ceramic according to Example 21 cylindrical samples with a diameter of 16 mm and a The thickness of 1.2 mm was 0.23.
Die gemäß Beispiel 21 bestimmte 3-Punkt-Biegefestigkeit der Glaskeramik betrug 272 ± 24 MPa.The 3-point flexural strength determined according to Example 21 Glass ceramic was 272 ± 24 MPa.
Hierzu wurden rechteckige Prüfkörper mit den Maßen 30 × 4 × 3 mm3 aus zweifach wärmebehandelten Massivblöcken gesägt. Der im Temperaturbereich von 100 bis 500 °C für diese Proben bestimmte Ausdehnungskoeffizient betrug 10,9 × 10-6 K-1.For this purpose, rectangular test specimens measuring 30 × 4 × 3 mm 3 were sawn from double heat-treated solid blocks. The coefficient of expansion determined for these samples in the temperature range from 100 to 500 ° C. was 10.9 × 10 -6 K -1 .
Die gemäß Beispiel 21 an Stäben aus zweifach thermischen behandelten Massivblöcken ermittelte Bruchzähigkeit betrug 2,1 ± 0,1 MPa √m.The according to Example 21 on rods made of double thermal The fracture toughness determined in the treated solid blocks was 2.1 ± 0.1 MPa √m.
Die gemäß Beispiel 21 an Proben von zweifach wärmebehandelter Glaskeramik bestimmte Säurebeständigkeit betrug 16 µg/cm2 und war damit deutlich unter dem Normwert für Dentalkeramikmaterialien von 2000 µg/cm2 und niedriger als der von konventionellen dentalen Gerüstmaterialien. The acid resistance determined according to Example 21 on samples of double-heat-treated glass ceramic was 16 µg / cm 2 and was thus clearly below the standard value for dental ceramic materials of 2000 µg / cm 2 and lower than that of conventional dental framework materials.
Auf die gefräste und zweifach wärmebehandelte Glaskeramik wurde schließlich eine transluzente bis transparente Sinterglaskeramik mit einem Ausdehnungskoeffizienten von 9,5 · 10-6 × K-1 schichtweise bei 760 °C und einer jeweiligen Haltezeit von 2 Minuten unter Vakuum aufgesintert. Dadurch entstand eine fertige dentale Restauration.Finally, a translucent to transparent sintered glass ceramic with an expansion coefficient of 9.5 × 10 -6 × K -1 was sintered in layers at 760 ° C. and a respective holding time of 2 minutes under vacuum on the milled and twice heat-treated glass ceramic. This resulted in a finished dental restoration.
In diesen Beispielen wurden heißgepreßte Glaskeramik-Produkte entsprechend Beispiel 21 hergestellt und auf ihre Eigenschaften überprüft. Als Ausgangsgläser wurden jedoch Gläser mit der in Tabelle I für Beispiele 1, 4, 18 und 20 angegebenen Zusammensetzung verwendet.In these examples, hot pressed glass ceramic products were used prepared according to Example 21 and their properties checked. However, glasses with the in Table I for compositions 1, 4, 18 and 20 given composition used.
Die für diese Glaskeramiken sowie die Glaskeramiken gemäß Beispiel 21 und 22 bestimmten Eigenschaften sind in Tabelle II aufgeführt. The properties determined for these glass ceramics and the glass ceramics according to Examples 21 and 22 are listed in Table II.
Claims (19)
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DE19750794A DE19750794A1 (en) | 1997-11-10 | 1997-11-10 | Process for the preparation of shaped translucent lithium disilicate glass-ceramic products |
DE19750794 | 1997-11-10 |
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EP0916625A1 true EP0916625A1 (en) | 1999-05-19 |
EP0916625B1 EP0916625B1 (en) | 2002-09-18 |
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EP (1) | EP0916625B1 (en) |
JP (1) | JP3088708B2 (en) |
AT (1) | ATE224341T1 (en) |
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DE59805597D1 (en) | 2002-10-24 |
EP0916625B1 (en) | 2002-09-18 |
CA2252660A1 (en) | 1999-05-10 |
JPH11314938A (en) | 1999-11-16 |
ATE224341T1 (en) | 2002-10-15 |
DE19750794A1 (en) | 1999-06-17 |
JP3088708B2 (en) | 2000-09-18 |
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